Materials Research.

2012; 15(2): 204-208 2012

DOI: 10.1590/S1516-14392012005000014

Characterization of Calcium Carbonate Obtained from Oyster and Mussel Shells

and Incorporation in Polypropylene

Michele Regina Rosa Hamestera, Palova Santos Balzera, Daniela Beckerb*

a
Instituto Superior Tupy IST, Rua Albano Schmidt, 3333, CEP 89206-001, Joinville, SC, Brasil
b
Departamento de Engenharia de Produo e Sistemas, Universidade Estadual de Santa Catarina UDESC,
Campus Universitrio Prof. Avelino Marcante, sn, Bom Retiro, CEP 89223-100, Joinville, SC, Brasil

Received: March 25, 2011; Revised: January 24, 2012

There is a high content of calcium carbonate in mussel and oyster shells, which can be used in the
formulation of medicine, in construction or as filler in polymer materials. This work has as its main
objective to obtain calcium carbonate from mussel and oyster shells and used as filler in polypropylene
compared their properties with polypropylene and commercial calcium carbonate composites. The
shellfish was milling and heated at 500C for 2hours. The powder obtained from shellfish were
characterized by scanning electron microscopy (SEM), X-ray fluorescence, particle size distribution
and abrasiveness and compared with commercial CaCO3 and mixed with polypropylene. The thermal
and mechanical properties of polypropylene with CaCO3 obtained from oyster and mussel shells and
with commercial CaCO3 were analysed. The results showed that CaCO3 can be obtained from oyster
and mussel shell and is technically possible to replace the commercial CaCO3 for that obtained from
the shells of shellfish in polypropylene composites.

Keywords: oyster shell, mussel shell, calcium carbonate, polymer

1. Introduction
Aquaculture is an important source of animal protein
for human consumption. In South America, Brazil is
second in production of shellfish, following Chile1. The
state of Santa Catarina is responsible for more than 90%
of Brazilian production of cultivated oysters and mussels.
Bivalve shellfish production consists in the cultivation of
the Mitilidae family represented by the pernaperna mussel
and the Ostreidae family, represented by the pacific oyster
Crassostreagigas2.
After harvest, the product for the market (the shellfish
meat) can go through a beneficiation process to improve its
appearance and add value. In these units, the mussels are
cooked by steaming or immersion and the shell is removed.
Of the entire amount of shellfish produced, 75 to 90%
consists of shells. These shells are composed of 95% calcium
carbonate, and the remainder is organic matter and other
compounds3. The mussel and oyster shells are discarded into
the environment. The improper disposal of solid waste from
shellfish cultivation decreases water oxygen and microalgae
that are responsible for the nutrition of mussels and oysters,
thus hindering the growth of these shellfish4.
Concern about the destination of oyster and mussel
waste is not only observed in Brazil. In Korea, for example
about 300,000t of oyster shells are generated annually. The
Korean government, concerned with public health, financed
a project to increase recycling of this waste, because if
this waste has been left untreated for a long time, it can
*e-mail: dep2db@joinville.udesc.br
be a source of nasty smell as a consequence of the decay
of flesh remnants attached to the oyster or the microbial
decomposition of salts into gases such as NH3, H2S and
amines5. Many studies have investigated the use of oyster-
shell waste as construction materials6-8. Another possibility
for reuse of these shells is to use them as supplementary
feeding9-11. Lee and co-workers12 demonstrated that crushed
oyster shells could be used as an alternative liming material
to restore soil chemical and microbial properties in upland
soil and to increase crop productivity.
Calcium carbonate is the most widely used filler
in terms of the number of applications in polymer. The
cheapest grades are low in price and are used primarily
to reduce costs. By contrast, the finest grades are an order
of magnitude higher in price and are used to modify
various properties, both during processing and in the final
compounds13. Some studies have investigated the use of
oyster-shell waste as filler in polymer14-15. Chongetal.14
prepared mixtures of recycled polyethylene (PE) and oyster-
shell powder, that was coated with ionic surfactant, to test
their fire-retardant properties. The mixtures present better
mechanical properties and fire-retardant behavior compared
with neat recycled PE. Funabashietal.15 evaluated method
of biomass carbon ration of polymer filled with calcium
carbonate using poly(butylene succinate) (PBS) with
oyster shell powder and poly (lactic acid) (PLA) with no-
biobased inorganic calcium carbonate. They observed that
the estimation method is effective for polymer composites
with CaCO3.
2012; 15(2) Characterization of Calcium Carbonate Obtained from Oyster and Mussel Shells and Incorporation in Polypropylene 205

The aim of this work is to obtain calcium carbonate from
seafood (mussels and oyster) shells and demonstrate that this
material can be reused as filler in polymer, based on thermal,
chemical and physical properties of calcium carbonate
and mechanical and thermal properties of polypropylene/
calcium carbonate composite.
2. Materials and Methods
The polypropylene (PP) and commercial calcium
carbonate used in this work were supplied by Braskem and
Crenor Carbonatos, respectively, under the tradename PP
H604 and Crenor MAX EB respectively. To obtain calcium
carbonate, mussel and oyster shells supplied by a restaurant
in Joinville, Brazil were used.
The mussel and oyster shells were heated in an oven
at 200C for 1 hour to make the shells more brittle and
submitted to milling in a high-speed planetary mill with a
porcelain jar and alumina balls for 15minutes with water.
The powders are heated again to 500C and maintained
for 2hours and to undo the clusters a new milling was
performed without water for 1minute. The powders were
characterized by particle size distribution analyses and
chemical composition using a laser diffraction analyzer
(CILAS 1064) and X-ray fluorescence (SHIMADZU
EDX-700).
Abrasiveness was analyzed using 100g of each sample
dissolved in distilled water and transferred into the test
cup. This cup was conected to a PVC roller which carries
174,000 rounds on the solution in contact with a grille
weighed in advance. After the test, the grille was weighed
again and the abrasiveness was determined by calculating
the mass difference before and after the test, relating to the
area subject to abrasion. This technique was performed in
an Einlehner AT 1000 device.
Polypropylene composite with commercial CaCO3
and mussel and oyster shells were prepared using a single
screw extruder (Ciola B50) set to a length/diameter equal to
25/1, screw rotation rate of 150rpm, with a flat temperature
profile along the barrel (180C). The composite composition
studied was 10wt.(%) of CaCO3 and 90wt.(%) of neat
PP. The composites were injected into a Sandretto Micro 65
injection-molding machine to obtain specimens for tensile
and impact tests. The injection molding was carried out with
a temperature in the nozzle of 200-225C.
The thermal degradation of the calcium carbonate and
composites was analyzed in a TA Instruments TG Q200
thermogravimetric analyser in a nitrogen atmosphere. Non-
isothermal analysis was performed in a temperature range of
25-800C, at 10C/min and nitrogen flow was maintained
at 50cm3/min.
Charpy impact tests, following ISO 179, were performed
on an EMIC Impact tester. Tensile tests, according to ISO
527 standards, were carried out in an EMIC universal testing
machine model. Crosshead displacement rate of 10mm/min
was used. A longitudinal strain gauge was used to obtain
the Young modulus.
The composites were analyzed by differential scanning
calorimetry (DSC) to determine the melting temperature,
percent of crystallinity and oxidation induction time (OIT).
The DSC tests were performed on equipment from TA
Instruments DSC Q20. The OIT analysis was conducting
according to ASTM D 3895-98. For determination of
melting temperature and percent of crystallinity, the samples
were heated at 10C/min under nitrogen atmosphere. The
percent of crystallinity (Xc) was determined from the
enthalpy of crystallization of PP, Equation1, using a value
of Hf=165J.g1 for isotactic PP 100%[16] crystalline and
the enthalpy values were corrected for PP weight present
in the composite.
H o
amostra
Xc = 100 (1)
H 0f
Changes in the morphology in the fracture surface during
the impact test of the PP/CaCO3 and CaCO3 morphology
were observed in scanning electron microscopy (SEM) Zeiss
DSM. The samples were first coated with a thin gold layer.
3. Results and Discussion
Table1 presents the chemical composition of commercial
CaCO3 and mussel and oyster shells. Mussel and oyster
shells present a slightly lower, although not significant,
amount of calcium oxide (CaO) than commercial calcium
carbonate. There are differences in chemical composition
because oysters and mussels are water filterer17. Kurunczi
and co-workers18, for example, detected mercury (Hg) and
lead (Pb) in mussel shells, because the water where these
mussels grew was contaminated. Chouetal.19 also detected
Pb in oyster shells in New Orleans. Mussel shells also
present a higher quantity of Fe2O3 than oyster shells, this
oxide can influence polymer oxidation when these shells
are used as filler in polymer matrix.
Figure1 presents commercial CaCO3, mussel and oyster
shell particle size distribution. It is possible to observe a
larger particle size distribution to oyster and mussel shells
(Figure1a,b respectively) than commercial CaCO3. This
behavior can be associated with a higher hardness of the
shells, because there is a higher concentration of silica in
the shells that increases shell hardness20 and the milling
conditions used was kept constant. Commercial calcium
carbonate grinding consists in several stages with different
grinding systems, until it reaches the average particle size
most appropriate to use13.
The MEV photomicrographs for commercial CaCO3,
mussel and oyster shell are shown in Figure2. It is
observed that both the oyster and mussel shells (Figure2a,b,
Table 1. Chemical composition of shellfish and commercial CaCO3.
Oxides Mussel (%) Oyster (%) CaCO3 (%)
CaO 95.7 98.2 99.1
K2O 0.5 - 0.4
SiO2 0.9 - -
SrO 0.4 - -
Fe2O3 0.7 - -
SO3 0.7 0.7 -
MgO 0.6 - -
Al2O3 0.4 - -
206 Hamester et al. Materials Research

respectively) contain higher concentration of fine particles
and there is also some presence of larger particles which
lead to more heterogeneous distribution compared to the
commercial CaCO3 (Figure2c). These results are also being
observed in particle size distribution curves of Figure1.
The shape of the oyster and mussel shells particles is more
irregular than commercial CaCO3.
The abrasiveness test showed that the commercial
CaCO3, mussel and oyster shells were 32, 28, 32g.cm2
respectively, showing no significant variation in this property
under the conditions tested.
Thermogravimetric analysis (TGA) and first derivative
TG curve [(d(TG)/dT) denoted by DTG] of PP/CaCO3
composites are shown in Figure3a,b and the data are
simplified in Table2. Although the oyster and mussel shells
contain other oxides in chemical composition, these did
not influence significantly the behavior of thermal stability
compared to the PP with commercial CaCO3. Composites
of PP with oyster or mussel presented higher temperature of
onset decomposition (dO) and maximum of decomposition
(doff).
Melting temperature (Tm), percent of crystallinity (Xc)
and oxidation induction time (OIT) of PP/CaCO3 composites
are shown in Table3. It can be noted that CaCO3 obtained
from mussel and oyster shells do not show any significant
difference in melting temperature and percent of crystallinity
compared to the composite with commercial CaCO3.
Oxidation induction time is lower for the composites
containing CaCO3 obtained from oyster and mussel shells
compared to the composite with commercial CaCO3. This
behavior can be explained by differences in chemical
composition of the fillers. The mussels showed 0.715%
Fe2O3, oyster shells less than 0.2% and in commercial
CaCO3, Fe2O3 was not detected. According Paoli21 transition
metal oxide (including iron) can catalyze polyolefin

Table 2. Degradation temperature of PP with oyster shell powder,

mussel shell powder and commercial CaCO3 from TG and DTG
curves.
Composites dO (C) doff (C)
PP/CaCO3 256 401
PP/mussel shell 306 416
PP/oyster shell 292 421
dO: temperature of onset decomposition. doff: temperature maximum of
decomposition.

Table 3. DSC results of PP with oyster shell powder, mussel shell

powder and commercial CaCO3.
Composites Tm (C) Xc (%) OIT (s)
PP/CaCO3 159 45 84
PP/mussel 159 50 14
PP/oyster 160 46 45

Table 4. Mechanical properties of PP with oyster shell powder,

mussel shell powder and commercial CaCO3.
PP/CaCO3 PP/oyster PP/mussel
Youngs Modulus
918 (58.1) 904 (40.4) 902 (49.6)
(MPa)
Yield strength
33 (1.4) 35 (0.6) 33 (1.0)
(MPa)
Elongation of break
61 (21.3) 38 (18.2) 26 (6.5)
(%)
Impact strenght
Figure 1. Particle size distribution of a)oyster and b)mussel shells; 3.2 (0.07) 3.4 (0.42) 3.4 (0.42)
(kJ.m2)
c)commercial CaCO3.
2012; 15(2) Characterization of Calcium Carbonate Obtained from Oyster and Mussel Shells and Incorporation in Polypropylene 207

oxidation. Allenetal.22 conducted a test on samples of
infrared PP containing silica which detected the presence
of carbonyl, evidence of oxidation; the authors argue that
the carbonyl formation is more associated with the presence
of aluminum, titanium and iron than the presence of silica.
Table4 summarizes the results for mechanical property
tests obtained for all samples studied. It is possible to
observe that PP composites with commercial CaCO3 and
those obtained from shellfish do not show any significant
difference on Youngs modulus, yield strength and impact

Figure 2. SEM micrographs of CaCO3 obtained from a)oyster and b)mussel shells; and c)commercial CaCO3.

Figure 3. a)TG curves and b)DTG curves of PP with oyster shell powder, mussel shell powder and commercial CaCO3.

AccV Spot Magn Det WD AccV Spot Magn Det WD AccV Spot Magn Det WD
10.0 kV 4.5 500 SE 10.1 50 m 7.0 kV 4.5 500 SE 10.1 50 m 7.0 kV 4.5 500 SE 10.1 50 m
(a) (b) (c)

Figure 4. SEM micrographs of impact test of PP with a)commercial CaCO3; b)mussel shells; and c)oyster shells.
208
strength. The composite with commercial CaCO3 showed
higher elongation at break than those composites with fillers
obtained from shellfish, which can be explained as being
due to the particle size distribution.
Sample fractures resulting from impact experiments were
analyzed by SEM, as shown in Figure4. In Figure4b,c that
display the micrographs of the composites with mussel and
oyster shells, we can see the large particles and many fine
particles of CaCO3 in the PP matrix, while the composite with
the commercial carbonate presented particles smaller and more
uniform. These differences can justify the smaller deformation
at break of PP with shellfish composites. No adhesion between
the domains in the matrix can be observed, probably due to
the weak interfacial bonding in all composites.
4. Conclusion
The results of this study showed that CaCO3 can be
obtained from oyster and mussel shells, since both have
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